Waxes



Patented Aug. 27, 1946 UNITED STATES PATENT OFFICE WAXES taszIeA-uer, South Orange, J.

No Drawings Application August 21, 1942,

Serial No. 455,613

r" claims. (CL 106-40) I FIELD or INVENTION This invention relates to the modification 0f the properties of Waxes. The invention is particularly concerned with treatment of organic ester-type waxes or waxlike materials, as distinguished from certain hydrocarbons which are sometimes termed waxes. For instance; while paraffin, montan wax and ceresin,ua're= sometimes referred'to as waxes, they are not true waxes. In contrast, the invention is concerned withthe treatment of ester-type waxes such, for instance, as listed just below:

Beeswax Carnauba wax Spermaceti wax Candelilla wax Japan Wax Bayberry (Myrtle) Wax These waxes are esters of long chain aliphatic alcohols with long chain aliphatic fatty acids, as is indicated in the following listing of some of the major constituents of various oi the: waxes above mentioned.

Beeswax a. Main constituents:-

1. Cerotic acid 2. Myricyl palmitate b. Subordinate constituents:

I. Melissic acid 2'. Myricyl' alcohol 3". Ceryl alcohol" c. 13% hydrocarbon C'arnaubuwas Carriaubic acid Ceryl, myricyl alcohols Other alcohols A hydroxy acid A hydrocarbon Spermaceti wax a. Main constituents:

1. Gem palmitate b. Subordinate constituents:

l. Glycerides of lauric, stea'ric, and myristic acids Ccmdelilla war" a. 56%unsaponifiable (hydrocarbon) b; Remainder (ester) J anon a. Main constituents:

1. Palm-itin 2. Palmitic acid b. Subordinate constituents:

L Dibas-ic' acids 2-. Soluble acids Bayberry was:

Although some of the'f'oregoing list'ar o'f ani- Inal and some of vegetable origin, I believe them all to be organicis'ocolloids, i. e., colloidal substances in which the dispersed phase and the dispersion medium are both of the same chemical composition; though present in different physical states: v i

There are other wax ,or wax-like materials which are organic; isoco'l-loi'ds andwhich may be treated in accordance with the invention'jfor instance, synthetic wax-11x6- products containing either a natural wax alcohol or a natural wax acid or their homologues, derivatives andsubstitution' products;

The term ester-typ waxes," as used herein, is intended to comprehend. not only the natural ester-type" waxes, but also synthetic products of the type in'entionedjust above; 1

I have found that bycispersing treating or frfod'iiyihg'ag'ehtsin tnevvaxes, changes may be brought about in" a number or different characteristics or properties, thereby rendering the treated waxes better suite'd'to many purposes than are'tne" same untreated wastes. The changes or nm'difications brought about in accordance with the present invention are apparently colloidal and/or chemical in nature, in many instances changes of both types occurriiig' as a result of the treatment. For instance, a change in tne relative proportions of the dispersed phase and dispersion medium may be brought about.

- Whatever may be the exact mechanism by which the changes occur, I have found thatthe present invention may be utilized to bring about changes in such physical characteristics as melting point, acid value, saponiiication value, iodine value, solubility characteristics in various solvents, and. physical consistency at various diiierenttemperatures Modification in certain respects noted above is important for some purposes, and for other purinstance, in fioor polish, furniture polish, shoe polish, and the like, it is frequently desirable to employ a wax having a relatively high melting 3 point. Although the melting point need not nec- 1essarily be changed in all instances, it is of importance that the invention is well suited to the raising of the melting point of waxes, for instance, of beeswax and certain others, which, in their normal condition have a relatively low melt- 1 ing point and therefore have not heretoforebeen' considered as practicable to employ for certain I purposes in which a higher melting point (for in- 1 stance, that of carnauba wax) is preferred. v The foregoing is cited as illustrative of the manner in which the present invention may be I utilized to adapt certain waxes to uses for which they are not well suited in their natural state.

preciable sacrifice of quality of finished-product such, for instance, as floor or furniture polish.

In addition to some of the uses'already mentioned, waxes are adaptable for many other purposes among which might be mentioned metal polishes, automobile body polishes, carbon paper and the invention, in its broad aspect, hasin mind adapting various waxes to the several commercial uses, thereby better fitting them for such purposes.

Before considering in detail the nature'of the process andthe treating agents employed, the

process is first briefly summarized as follows:

The wax to be treated is preferably heated in I the presence of the modifying agent for a sub- In this way, in some instances the invention 3 makes possible the utilization of a less expensive wax to replace a more expensive one, without apstantial period of time and at a temperature con- V siderably above normal room temperature, it being of importance to secure thorough dispersion of the treating agent in the wax.

Moorr'vmc AGENTS Modifying agents of 'quite'awide variety of molecule, or capable of orientin their different radicals in opposite directions on an interface of liquid-gas, solid-gas, liquid-solid or liquid-liquid.

Many polar compounds which are electrolytes have been found to be useful.

The modifying agents may be classified in various Ways, for instance under the following headings-- Metal salts of inorganic acids Metal salts of organic acids Inorganic acids Organic acids Metallo-organic compounds:

Metal alcoholates Aryl-metal compounds Organic salts of inorganic acids Inorganic salts of organic bases Organic esters Amines also constitute a useful class, particularly the poly-amines, for instance, di-amines.

Many of the compounds falling in certain Typical examples of certain of the foregoing classifications are given just below:

Metal salts of inorganic acids: Sodium bisulphite Sodium 'hydrosulphite Sodium sulphite Ammonium iodide Magnesium chloride Zinc carbonate Lead chromate Metal salts of organic acids:

Sodium oxalate 7 G-salt (sodium beta nate) Salts of organic amines:

Diphenylamine trichloracetate Inorganic acids:

Sulphuric acid Phosphoric acid' .Hydrochloric acid Organic acids:

Tartaric acid Maleic acid Acetic acid Oxalic acid Salicylic acid Phthalic acid Citric acid Metal alcoholates: Sodium amylate Amines:

Benzidine base a-Naphthylamine naphthol-fi, S-disulpho- V 'Iwo-radical compounds:

Sulphosalicylic acid Nitro-anthraquinone p-Toluene sulphochloride p-Toluene sulphonic acid o-Nitrophenol p-Nitrophenol I have found certain groups of modifying agents to be particularly effective in the treat ment of waxesfor instance, metal salts; amines, particularly diprimary amines; and two radical type compounds, especially those containing sulphoand nitro-grcups.

Hereinafter examples are given of the treatment of waxes with modifying agents selected from various of the classes above discussed.

TREATMENT CONDITIONS Although the treatment conditions may be varied in accordance with a number of factors such as the particular wax being treated, the

treating agent selected and the characteristics desired, in general, the treatment conditions should conform with the following:

With respect to temperature, it is first noted that while some modification may be brought about by dispersing the modifying agent in the wax at normal room temperature, in general, the

treatment temperature should'be above the meltin temperature is usually accompanied b more 5 rapid and/or more extensive modification, although as just noted, the temperature is desirably kept below the point at which any decomposition occurs. Particularly good results are secured with many waxes at temperatures between 0 about 250 C. and 310 C.

The duration of the heating will again depend somewhat on the materials used and the results desired. Usually the heating should be continued at least until thorough dispersion of the treating agent is obtained. Ordinarily it is found that treatment for a period of at. least 30 minutes is required for this purpose.

. The quantity of modifying agent employed will also depend somewhat, on the Wax being treated,

examples given hereinafter, .5% is shown to be sufiicient for some purposes.

The nature of the atmosphere in contact with the reaction mass will influence the modification which occurs. With many waxes and with treatments for a number of purposes, it may be found 3 desirable to exclude air from the reaction. This may be accomplished by employing vacuum, and/ or introducing certain gases into the reaction vessel to blanket the surface of the batch. Gases Ordinarily, however, a range 25 and treating agent together. Obviously, however, from the standpoint of the broader aspects of the invention, the wax and the treating agent may be brought together in any desired manner. Agitation may be useful for this purpose in some instances.

Beyond the foregoing, it is contemplated that the modifying agent may be produced in siti, by introducing materials which will react under the conditions of treatment to produce the modifying agent desired.

EXAMPLES In a series of comparative experiments, a bees-- wax wa treated with a number of different modifying agents. The initial untreated beeswax had a melting point of 64 C., an acid value of 20.2 and a saponification value of 93.3. The wax was of medium light color.

For purposes of comparison, in one experiment this wax was heated without any modifying agent, under exactly the same conditions as em ployed for the heating in the following experiments using various dififerent modifying agents. This heated wax had a melting point of 75 0., an acid value of .75, and a saponification value of 100.5. The product was black.

The treatment conditions employed not only for the heating of the wax without modifying agent, as above mentioned, but. also in each of the following experiments of this series were as follows:

The wax was placed in an open beaker under a blanket of CO2 and maintained, at about 300 C.

5 for a period of five hours.

The following table indicates the modifying agents and percentages thereof used in each of the comparative experiments, and also various of the resulting characteristics:

. Per- Melting Acid Sap. Solu- Example Modm mg agent cent point value value bility C. Untreated 64 20 .2 93 .3 l Heated 75 .75 100 .5 ,1 1a- Sodnlm bisulphite A 82 2 .75 96 .4 1+ 1b 5 137 1.95 77 .5 2+ 2 Sodium hydrosulph1te y, 75 1 .15 89 .7 1 2b 5 140 2 .8 66 .7 4+ 3 Sodium sulph1te y, 90 l .75. 79 .9 1 4 Benzidine base. V 75 1 .98 88 .1 I 4z, o 5 121 .7 92 .4 2+ 5a N itro-anthraquinone 73' .7 91 .85 1+ 51;, do 5 74 .7 83.2 2- ea Sulphosalicylic acid M, 76 .7 92 .8 1 6b .do; 5 75 .8 100.5 1. 7 p-Toluene sulphochlo .3 89.7 1+ 71; do 5 68 54.5 85.5 1+ p-Toluene sulphonic acid 75 0 .8 92 .6 l d 6 2.1 74 .4 3+ 75 .7 100 .6 1 5 74 4 .9 92.5 1 74 .8 94 .6 l 5 75 4 .03 .8 l

suitable for this purpose are nitrogen, CO2, S02, H28, amongst others.

Pressures above atmospheric may also be employed to advantage for some purposes.

In addition to employment of gases for purposes such as mentioned just above, certain gases may also be utilized by bubbling the same through 65 materials at normal room temperatures, admixture of the wax and modifying agent is, inmost" com- 70 60 classes of treating agents are of especial advantage in raising the melting point of the waxes. Note for instance that a very marked increase in melting point is secured by the use of metal salts (see 'Examples 1a, 1b, 2a, 2b and 3a) and also by the use of an amine,such as the benzidine base of. Examples 4a and 41), this amine being a diprimary amine.

Analysis of the foregoing table will further show that in many instances the higher percentage of modifying agent produces a greater degree of modification. v

The comparative results above also indicate the. possibility ofsecuring' appreciable changes cases, desirably accomplished by melting the wax 75' not only in acid value but also in the saponification value, depending upon the treating agent employed and the percentage used.

The column in the above table under the heading of Solubility indicates the consistency of a mixture of the wax with turpentine, in the ratio of 50% wax and 50% turpentine. The numerals P in the column represent an arbitrary scale, the higher numerals indicating stiffer wax-turpentine mixtures. For example, numeral 2 indicates a mixture of stiffer consistency than numeral 1.

2+ indicates a still stiifer mixture, and so forth.

Thus/from the Solubility column it will be seen that most of the treated waxes yield waxturpentine mixtures which are at least as stiff as ing agent) those secured with the untreated wax (and also with the wax which was heated without modify- Many of the modified waxes yielded wax-turpentine mixtures considerably stiffer than the same mixture incorporatingthe untreated wax; note, especially, the waxes treated with j of sodium hydrosulphite and with 5% of p- 3 material. sired to retain as light a color as possible, the modifyingagent should be selected accordin ly.

toluene sulphonic acid. 9

Although the color of all of the products was darker than the untreated and unheated beeswax, 1 it is interesting to note that the color of certain 3 of the products resulting from use of modifying agents was lighter than the color of the beeswax which had been heated without modifying agent. Thus, the products of Examples 4a, 6a, 6b, 7a., 7b, 8a and 9a were all lighter in color than was the 1 product of the beeswax when cooked without modifying agent.

With respect to the color of the waxes, it is to be noted that for many purposes the color is im- In instances, however, where it is de- In another series of comparative experiments same for each example. In this series-treatment was eifected in a closed beaker (having only a small outlet to the atmosphere), without intro 1 duction of any gas and at atmospheric pressure.

, The temperature was maintained in each case at- 1 about 300 C. for five hours. of this group 5% of the treating agent was em-- I ployed.

'In all experiments candelilla wax was treated with various modify "ing agents, the treatment conditions being the The initial untreated candelilla wax had a 1 melting point of 73, an acid value of 16.9, saponi fication .value of 52.5, the initial color being medium light.

For purposes of comparison one batch of they The following table indicates the reagent used in the several experiments of this series, and also 1 various characteristics:

I 'wax was trea ed under the foregoing conditions f but without the presence of any modifying agent. "i The product of this experiment had a' melting 1 point of '74" C., an acid value of 9.9, a saponifica- 3 tion value of 48, and the color was medium dark.

' wax-turpentine mixtures, this again being indicated in the Solubility column.

' Examples 14 and 17 yielded a product having a color approximating that of the original untreated and unheated candelilla wax.

The above table also shows considerable modification in certain instances in-the consistency of characteristic Various of the foregoing waxes were incorporated in several different polishformulas in order to secure comparative data as between treated and untreated waxes and also as between the effect of different modifying agents. With this purpose in view th waxes were used in a furniture polish, in a floor polish and in.a shoe polish.

Furniture polish A typical furniture polish formula was selected,

this being as follows (all parts being by weight) "Replacement ingredient 10 Beeswax 4 Ceresin '4 Stearic acid 8 Triethanolamine 4.8 V. M. & P. naphtha Water (boiling) 200 Varnish makers and painters naphtha.

In formulating the foregoing polish, the several wax ingredients (including stearic acid) were melted'in the order listed above, the freplacement ingredient being different .in each polish prepared, i. e., being selected from various of the untreated and treated waxesdiscussed above. After melting of the waxes together, the triethanolamine was added. Then followed slow addition of the naphtha with agitation. Agitation was continued during very slow addition of the boiling water, until a uniform'emulsion was produced, the

fa'gitation being continued until the polish had cooled. Q 'The untreated and also the heated (without modifying agent) beeswax and candelilla wax were substituted in plaoeof the replacement ingredien in addition to the employment of various of the waxes modified with treating agents. For convenience in the following analysis of re- Example Modifying agent gag Acid value 553;, g gg Color Degrees Untreated 73 52. 5 l L1ght. I i 48. 0 l Fairly dark.

Sodium bisu1phite 16. 9 3+ Black. Sodium hydrosulphite 22.0 1+ Quite dark. Benzidine base 29.3 4+ Black. Nitroanthraquinon 25.1 V 1- Light.

Sulphosalicylic acid" 46.4 1 Fairly dark. p-Toluene sulphochloride 39. 6 1 Do. p-Toluene sulphonic acid 29. 1 1+ Quite light. o-Nitrophenol 7 33.1 1 Very dark. p-Nitrophenol 89 do 40. 7 1+ Black. 7

sults, the beeswax which was used in untreated condition and the beeswax which was heated without modifying agent are referred to, respectively as beeswax controls A and B. The candelilla wax (untreated, and heated without modifying agent) are similarly referred to as candelilla controls A and B.

This series of furniture polish experiments showed some very interesting improvements as'a result of the use of modifying agents, as compared with the several controls; and while adjustment of other ingredients in the formulation would normally be desirable, for properly balanced polishes when one 'Wax is substituted for another, the formulation was kept the same throughout the series of experiments in order to clearly demonstrate the effect of substitution of the modified wax for the unmodified wax.

Various characteristics of the polishes were then determined and compared. The following are some of the more important improvements which were noted.

First, with respect to the beeswax furniture polishes, many of them indicated an improvement both with respect to'rubbing qualities and with respect to stability (stability of the emulsion).

Thus, polishes prepared with waxes treated with sodium bisulphite, sodium hydrosulphite, benzidine base, nitroanthraquinone, all disclosed improved rubbing qualities, as compared with both of the beeswax controls A and B.

The stability of the polishes prepared with modified beeswax also compared very favorably with the beeswax controls, most of the polishes showing up better in this respect than the beeswax control A, many also being equivalent to beeswax control B.

The gloss of the modified beeswax polishes also compares favorably with the controls, beeswax treated with sodium bisulphite, being marked- 1y better than both of the controls A and B.

With respect to the use of candelilla wax, it is noted that various of the polishes containing modified candelilla wax showed improvement in rubbing qualities and stability of the emulsion as compared with candelilla controls A and B. The metal salts showed particularly good results with respect to rubbing qualities and stability, especially sodium bisulphite and sodium hydrosulphite.

Although there was considerable variation in color as between the Various polishes, it may be mentioned that o-nitropheno-l and sulphosalicylic acid, both with beeswax and with candelilla wax yielded polishes of quite light color.

Floor polish The following formula was selected for purposes of testing the several In formulating the foregoing polish, portion A is prepared by first melting the "replacement ingredient, i. e., the wax, and then adding the oleic acid. The temperature is brought to 95 C.

waxes in a floor polish.

10 and the triethanolamine is slowly added, with constant stirring. Next the borax of part A was dissolved in one-quarter of the water (heated to boiling), and this borax solution was then added to the wax solution. The resulting mass was stirred for two minutes, after which the remainder of the water (of part A) was added and the mixture stirred until cold.

Part B was prepared by boiling the first part of the water thereof and then dissolving the borax therein, after which the shellac was added to the borax solution with stirring. Finally the remainder of the water (boiling) was added.

Preferably after permitting the solutions (A and B) to stand for a day, 18.5 parts of B are added to 100.9 parts of A, with stirring.

As in the experiments with furniture polish, various of the modified and unmodified waxes were substituted in the position of the replacement ingredient, and the polishes were then analyzed for various characteristics, for purposes of comparison.

Here again, not withstanding the fact that for properly balanced polishes when one wax is substituted for another the formulation would ordinarily be altered, in order to secure better comparisons, the formula was kept the same in each instance, thereby clearly demonstrating the effect of substitution of the modified waxes for the unmodified waxes.

Numerous of the fioor polishes made with modified waxes showed improvements over polishes made wit the beeswax and candelilla wax controls A and B.

With respect to ease of emulsification, it is first noted that most of the modified beeswaxes were at least equal to or better than the beeswax controls A and B. Moreover, certain of the modifying agents yielded polishes in which the emulsion stability was at least equal to or better than the controls. Sodium bisulphite and sulphosali- ,cylic acid were both effective in yielding good stability characteristics.

With respect to the properties just mentioned, the polishes made with modified candelilla wax also showed up in a similar way. Sulphosalicylic acid showed good results not only from the standpoint of ease of emulsion and stability of emulsion, but also with respect to polish or gloss secured. This reagent (sulphosalicylic acid) was in fact particularly good with respect to gloss.

Shoe polish The shoe polish formula employed for test purposes was as follows (all parts being by weight) In preparing the shoe polishes, the replacement ingredient (the wax) was first melted after which the montan, beeswax and paraffin were added. Then, with agitation the turpentine was added. Here again, both the beeswax and candelilla controls A and B, as well as the modified waxes, were substituted in the position of the replacement ingredient.

The results with the beeswax polishes indicated that almost all of the polishes made with modified beeswax were at least harder than beeswax controlA, and in some instances, even appreciably harder than beeswax control B.

With respect to gloss, improvement was noted with most of the polishes made with modified ishes' than those with of 11 beeswax; sodium blsulphite, sodium hydrosulphlte and p-toluene sulphochloride yielding polishes of particularly good gloss in comparison with the controls.

' With respect to polish consistency, it is worthy of note that ingeneral the waxes treated with /2% of the modifying agents yielded harder polmodifying agent. However, the metal salts showed up well with respect to consistency, even where used in 5% concentration; 5% sodium bisulphite and 5% sodium hydrosulphite both yielding quite hard polishes in comparison with the beeswax controls A and B. a

LMany of the polishes made with modified candelilla wax also showed up satisfactorily with respect to consistency and gloss, sodium bisulphite being particularly good for both of these characteristics. p-Toluene sulphochloride also yielded notably improved viscosity (a harder paste) than did the candelilla controls A and B. 1 I claim:

1. The process of modifying at least one of the following physical properties of ester-type waxes: consistency, melting point, rubbing characteriswax from 0.5% to 10% of a compound having within the molecule an acidic inorganic residue and an organic residue and heating the wax to a temperature between about 100 C. and the 'addition'of at least one of the group consisting fof hydrogen atoms, O-H-groups, and water molecules, said'modifying agent being a member of the class consisting of aromatic sulfonic acids,

aromatic sulfochlorides, and nitro-substituted of claim 1, in which said wax and a volatile dispersion medium and being characterized by a materially greater film toughness than characterizes a polish film made from the same ingredients but in which the waxis modified, said modified wax product comprising thereaction product of av natural ester-type wax 1 with from 0.5% to 10% ofa compound having tics, which process comprises dispersing in the 'sulfonic acids, aromatic decomposition point of the wax, until the wax "manifests properties which are substantially different in .at least one of the respects herein named, as compared to the properties of a similar material subjected to the same treatment but absence of the treating compound, said treat- :ing compoundbeing a member of the class conlsisting of aromatic sulfonic acids, aromatic sulfochlorides, and nitro-substituted aromatic "compounds, capable of yielding an inorganic acid which is a'member of the group consisting of sulfuric acid, chlorsulfonic acid and nitric acid under the conditions of the treatment. Y

2. The process in accordance with claim 1' in which the treatment temperature is from about 250 C. to 310 C. V 7 a 3. The process which comprises dispersing from 0.5% to 10% of a compound in an ester- 7 type wax and heating the wax and treating compound to atemperature between about 100 C. and the decomposition point of least 30 minutes to modify the solubility of the the wax 'for at wax in organic solvents, which process is characterized in that the treating compound employed comprises an acidicinorganic residue and 3 an organic residue, said inorganic residue'being capable of yielding an inorganic acid upon the within the molecule an acidic inorganic residue and an organic residue, and said compound being a member of the class consisting of aromatic sulfochlorides, and nitro-substituted aromatic compounds.

8. A heat-treated ester-type natural wax having dispersed therein from 0.5% to 10% of a treating compound having within the molecule an acidic inorganic residueand an organic residue, said wax having a melting point, appreciably higher than that of the same natural wax heat- 7 treated alone, and said treating compound being a member of the class consisting of aromatic sulfonic acids, aromatic sulfochlorides, and nitro substituted aromatic compounds. 7 I

9. A polish comprising, as wax ingredient, the

modified wax product of claim 8, and manifesting an increased hardness in its final films, as compared to a polish made in the same way and from the same ingredients but in which-the wax com ponent does not comprise a treating compound, said polish also containing water as volatile dispersion medium.

10. A polish comprising, as wax ingredient the modified wax product of claim 8. and manifesting an increased hardness in its final films, as compared to a polish made in the same way and from the same ingredients but in which the wax component does not comprise a treating com.- pound, said polish also containing an organic solvent as volatile dispersion medium.

LASZLO AUER. 

